Skin-whitening cosmetic

ABSTRACT

A skin-whitening cosmetic material which contains an unsaturated fatty acid or a derivative thereof as the active ingredient, is highly effective in making the color of pigmentation on the skin lighter at a lower concentration, and is highly safe. The skin-whitening cosmetic material comprises (A) at least one member selected from unsaturated fatty acids having from 18 to 22 carbon atoms and having from 2 to 6 double bonds in the molecular structure, and derivatives thereof, (B) a phospholipid, (C) an antioxidant, (D) at least one member selected from proteins and hydrolyzates thereof, and (E) at least one member selected from muco-polysaccharides and salts thereof.

This application is a 371 of PCT/JP98/02548 filed Jun. 9, 1998.

TECHNICAL FIELD

The present invention relates to a skin-whitening cosmetic material withwhich skin blackening or skin pigmentation such as spots and frecklesdue to UV rays is removed, reduced (whitened) or prevented.

BACKGROUND ART

Dyspigmentation is one symptom of skin aging, which gives spots such aschloasmata (liver spots) and senile spots. It is known thatdyspigmentation is exacerbated by ultraviolet rays. To preventdyspigmentation, used are UV protectors. To relieve dyspigmentationwhich has already produced spots, used are skin-whitening cosmeticmaterials comprising, as the active ingredient, any of vitamin C,placenta extract, kojic acid, arbutin, unsaturated fatty acids, etc. Ofthose, it is known that unsaturated fatty acids such as typicallylinoleic acid or linolic acid have an excellent effect of reducing orwhitening pigmentation caused on the skin (see the Journal of theCosmetician Association of Japan, Vol. 27, pp. 415-423, 1993).

However, skin-whitening cosmetic materials comprising unsaturated fattyacids such as linoleic acid or linolic acid are problematic in that theendermic absorption of unsaturated fatty acids having been applied tothe skin is often prevented by the barrier function of the skin with theresult that the skin-whitening cosmetic materials applied to the skincould not exhibit so much the effect of reducing or whiteningpigmentation to the degree as expected. Therefore, in order to make themexhibit a high skin-whitening effect, skin-whitening cosmetic materialsmust contain a large amount of unsaturated fatty acids, but causeunfavorable skin troubles.

Some reports are known, which disclose emulsified cosmetics (seeJapanese Patent Application Laid-Open (JP-A) Hei-5-70332) or linimentsfor external use (JP-A Hei-5-70334) comprising unsaturated fatty acids,phospholipids, and proteins or their decomposates; and skin-treating andprotecting agents comprising unsaturated fatty acids, phospholipids andvitamin E (see JP-A Sho-61-40210). However, the skin-whitening effect ofthose known materials is poor.

On the other hand, it is well known that liposomes are effective ascarriers. For example, known are liposomes comprising linoleic acid orlinolic acid as the active ingredient, which are said effective foracne, blackheads, pimples, pustules, etc. (see Published Japanesetranslation of PCT international publication for patent application(JP-W) Hei-7-509001). However, the stability of the cosmetic materialscomprising such liposomes is not satisfactory, and the effective amountof linoleic acid or linolic acid to be in those liposomes is at least 1%by weight or more. Thus, it is hard to say that know liposome exhibit asufficient effect at a low concentration of the active ingredient.

Accordingly, an object of the present invention is to provide askin-whitening cosmetic material which comprises, as the activeingredient, an unsaturated fatty acid or a derivative thereof, which ishighly effective for reducing or whitening pigmentation caused on theskin even in a lower concentration of the active ingredient and ishighly safe.

DISCLOSURE OF THE INVENTION

We, the present inventors have assiduously studied in order to attainthe object noted above, and, as a result, have found surprisingly that askin-whitening cosmetic material comprising phospholipids, antioxidants,proteins or their decomposates, muco-polysaccharides or their salts,along with unsaturated fatty acids such as linoleic acid or linolic acidexhibits an excellent effect for reducing or whitening skin spots eventhough it contains a reduced amount of unsaturated fatty acids, and thatthe safety of the material is high. On the basis of these findings, wehave completed the present invention.

Specifically, the invention provides a skin-whitening cosmetic materialcomprising;

(A) at least one member selected from unsaturated fatty acids havingfrom 18 to 22 carbon atoms and having from 2 to 6 double bonds in themolecular structure, and their derivatives,

(B) a phospholipid,

(C) an antioxidant,

(D) at least one member selected from proteins and their hydrolyzates,and

(E) at least one member selected from muco-polysaccharides and theirsalts.

Preferably, the skin-whitening cosmetic material of the inventioncomprises liposomal composites of those ingredients (A) to (E).

The invention also provides a skin-whitening cosmetic materialcomprising liposomal composites of the ingredients (A) to (E).

BRIEF EXPLANATION OF DRAWINGS

FIG. 1 is a graph showing the relationship between the period of timeafter application of samples of a skin-whitening cosmetic material tothe skin, and the skin-whitening effect of the samples.

FIG. 2 is a graph showing the relationship between the period of timeafter application of samples of a skin-whitening cosmetic material tothe skin, and the degree of penetration of the unsaturated fatty acidsin the samples into the skin.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the invention is described in detail herein under.

The unsaturated fatty acids and their derivatives to be used as thecomponent (A) in the cosmetic material of the invention have from 18 to22 carbon atoms in the fatty acid moiety and from 2 to 6 double bonds inthe molecular structure. The fatty acids of that type include, forexample, free unsaturated fatty acids, such as linoleic acid or linolicacid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid,arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, etc.;metal salts of unsaturated fatty acids, such as sodium linoleate,potassium α-linolenate, etc.; amino acid salts of unsaturated fattyacids, such as arginine linoleate, lysine α-linolenate, etc.; aminesalts of unsaturated fatty acids, such as triethanolamine linoleate,monoethanolamine α-linolenate, etc.; and mono-esters and di-esters ofunsaturated fatty acids, such as ethyl linoleate, ethyl a-linolenate,linoleic acid monoglyceride, α-linolenic acid monoglyceride, linoleicacid diglyceride, α-linolenic acid diglyceride, etc. Triglycerides ofunsaturated fatty acids existing in ordinary vegetable oils and fats areexcluded. Of those fatty acids, preferred are linoleic acid or linolicacid, α-linolenic acid, ethyl linoleate, ethyl α-linolenate, linoleicacid monoglyceride, and α-linolenic acid monoglyceride, and especiallypreferred is linoleic acid. One or more of those unsaturated fatty acidsand their derivatives may be in the composition.

The amount of the unsaturated fatty acids and their derivatives to be inthe cosmetic material of the invention may be from 0.01 to 0.7% byweight, preferably from 0.03 to 0.5% by weight, and most preferably from0.05 to 0.3% by weight. If the amount is smaller than the defined range,the effect of the cosmetic material to reduce or whiten pigmentation maybe unsatisfactory. However, even if the amount is larger than thedefined range, the effect of the cosmetic material tends to be no moreaugmented.

The phospholipids of the component (B) include, for example, naturallecithins, such as phosphatidyl choline, phosphatidyl serine,phosphatidyl ethanolamine, phosphatidyl inositol, phosphatidyl glycerol,sphingomyelin, soybean lecithin, corn lecithin, cotton seed oillecithin, egg yolk lecithin, egg white lecithin, etc.; hydrogenatedlecithins; and phospholipid derivatives as formed by introducingpolyethylene glycol or aminoglycans into those phospholipids. One ormore of those phospholipids may be in the composition. Of thosephospholipids, preferred are soybean lecithin, egg yolk lecithin,hydrogenated soybean lecithin, and hydrogenated egg yolk lecithin.

The amount of the phospholipids in the cosmetic material may be from0.05 to 10% by weight, and preferably from 0.20 to 2% by weight. If theamount is smaller than the defined range, the effect in reducing orwhitening pigmentation may not be found. Even if the amount is largerthan the defined range, the effect of the cosmetic material tends to beno more augmented.

The antioxidants of the component (C) include, for example,dibutylhydroxytoluene, butylhydroxyanisole, vitamin E and itsderivatives, vitamin C and its derivatives, erythorbic acid and itssalts, vegetable extracts such as cranesbill extract, hamamelis extract,tea extract, etc., and gallates. Of those, preferred are vitamin E,dibutylhydroxytoluene, butyl-hydroxyanisole, and gallates, andespecially preferred is vitamin E. One or more of those antioxidants maybe in the composition. The amount of the antioxidants in the cosmeticmaterial may be from 0.005 to 0.5% by weight, and preferably from 0.01to 0.2% by weight. If the amount is smaller than the defined range, theeffect of the cosmetic material to reduce or whiten pigmentation may notlast long. On the other hand, if the amount is larger than the definedrange, the stability of the cosmetic material may be lowered.

The proteins and their hydrolyzates of the component (D) for use in theinvention include, for example, collagen, elastin, keratin, casein, andtheir hydrolyzates, salts of such hydrolyzates, esters of suchhydrolyzates, and enzyme-processed proteins and protein hydrolyzates. Ofthose, preferred are collagen, elastin and their hydrolyzates, salts ofsuch hydrolyzates, and esters of such hydrolyzates, which include, forexample, hydrolyzed collagen, atelocollagen, hydrolyzed sodium casein,hydrolyzed ethyl collagen, and water-soluble collagen. One or more ofthose proteins and their hydrolyzates may be in the composition. Theamount of the component (D) maybe from 0.001 to 0.5% by weight, andpreferably from 0.01 to 0.1% by weight. If the amount is smaller thanthe defined range, the effect in reducing or whitening pigmentation maynot be found. If the amount is larger than the defined range, the effectof the cosmetic material tends to be no more augmented.

The muco-polysaccharides of the component (E) include, for example,chondroitin sulfate, hyaluronic acid, dermatan sulfate, heparan sulfate,mucoitin sulfate, heparin and its derivatives, and their sodium saltsand potassium salts. Of those, preferred are chondroitin sulfate,hyaluronic acid and their sodium salts. The muco-polysaccharides may bederived from natural substances or may be produced in biochemicalmethods. One or more of those muco-polysaccharides may be in thecomposition.

The amount of the muco-polysaccharides may be from 0.0005 to 0.5% byweight, and preferably from 0.001 to 0.1% by weight. If the amount issmaller than the defined range, the cosmetic material may be ineffectivein reducing or whitening pigmentation. If the amount is larger than thedefined range, the feel of the cosmetic material may be worsened.

Production of Cosmetic Material:

To produce the skin-whitening cosmetic material of the invention, theingredients (A) to (E) noted above may be mixed and formulated in anyordinary manner, according to the intended form of the cosmeticmaterial, to give ordinary formulations of milky lotion, cream, lotion,essence, cleansing, pack, face wash, etc.

Alternatively, a liposomal composite containing the components (A) to(E) is previously prepared, and it may be formulated to give desiredformulations. Using the liposomal composite is preferred, since itproduces a high skin-whitening effect even though the concentration ofthe active ingredients therein is low and since the stability of theactive ingredients therein is increased so that the cosmetic materialcomprising it is hardly deteriorated.

(a) In the invention, a first method of producing the liposomalcomposite comprises forming liposomes that contain the component (A) ofunsaturated fatty acids and their derivatives, the component (B) ofphospholipids and the component (C) of antioxidants of the indispensableingredients, followed by dispersing and mixing the resulting liposomesin a mixture comprising the component (D) of proteins and theirhydrolyzates and the component (E) of muco-polysaccharides. This methodis hereinafter referred to as Method A.

(b) A second method of producing the liposomal composite comprisesforming liposomes that contain the component (A) of unsaturated fattyacids and their derivatives, the component (B) of phospholipids and thecomponent (C) of antioxidants, in a mixture comprising the component (D)of proteins and their hydrolyzates and the component (E) ofmuco-polysaccharides. This method is hereinafter referred to as MethodB.

In one preferred embodiment of the invention, a liposomal compositecontaining the indispensable ingredients noted above is first preparedand then formulated into desired formulations of a skin-whiteningcosmetic material. Especially preferred is mixing and dispersing theliposomal composite in cosmetic media. For this, preferred arewater-soluble cosmetic media. Examples of this embodiment includecosmetic lotions, gels, essences and oil-in-water emulsions.

Preparation of Liposomal Composite:

Now, preferred methods for producing liposomal composites to be in thecosmetic material of the invention are illustrated hereinunder, which,however, are not limitative.

Method A

Liposomes containing the component (A) of unsaturated fatty acids andtheir derivatives, the component (B) of phospholipids and the component(C) of antioxidants are prepared according to any of the methods (1) to(4) mentioned below.

(1) A phospholipid, an unsaturated fatty acid or its salt or ester, andan antioxidant are homogenized, and then hydrated with an aqueoussolution containing a pH-adjusting agent, a polyhydric alcohol, asaccharide and the like, to give liposomes containing the unsaturatedfatty acid or its salt or ester.

(2) A phospholipid, an unsaturated fatty acid or its salt or ester, andan antioxidant are dissolved in an alcohol or polyhydric alcohol, andthen hydrated with an aqueous solution containing a pH-adjusting agent,a polyhydric alcohol, a saccharide and the like, to give liposomes.

(3) Using an ultrasonic wave generator or a French press, aphospholipid, an unsaturated fatty acid or its salt or ester, and anantioxidant are complexed in water to give liposomes.

(4) A phospholipid, an unsaturated fatty acid or its salt or ester, andan antioxidant are mixed and dissolved in ethanol, then the resultingethanolic solution is added to an aqueous solution of potassiumchloride, and thereafter ethanol is removed from the resulting mixtureto give liposomes.

The liposomal dispersion thus prepared is, if desired, passed through afilter to dress the liposomes. Also if desired, any of polymersubstances such as carboxyvinyl polymer, carboxymethyl cellulose,hydroxyethyl cellulose, xanthane gum,poly(oxyethylene)-poly(oxypropylene) block copolymer, etc.; pH-adjustingagents such as citric acid, salts of citric acid, phosphoric acid, saltsof phosphoric acid, triethanolamine, potassium hydroxide, sodiumhydroxide, lactic acid, salts of lactic acid, etc.; polyhydric alcoholssuch as glycerin, propylene glycol, butylene glycol, etc.;polysaccharides such as salts of alginic acid, esters of alginic acid,etc.; saccharides such as trehalose, glucose, sorbitol, sucrose, etc.;and cholesterol may be added to the liposomal dispersion in order toimprove the stability of the dispersion.

The ratio of the unsaturated fatty acid or its salt or ester to thephospholipid to form liposomes is preferably from 1/5 to 2/1 by mol,more preferably from 1/2 to 3/2 by mol, as the liposomes comprising themin the ratio falling within the defined range produce a higherskin-whitening effect.

Preparation of Liposomal Composite:

Next, the liposomal dispersion as prepared according to any of themethods noted above is dispersed in an aqueous solution comprising aprotein or its decomposate and a muco-polysaccharide. Thus is obtained aliposomal composite containing a phospholipid, an unsaturated fatty acidor its salt or ester, an antioxidant, a protein and amuco-polysaccharide.

Method B

A second method of producing the liposomal composite for use in theinvention comprises forming liposomes that contains the components (A),(B) and (C) in a mixture containing the components (D) and (E), forexample, as in the following methods (1) to (3).

(1) A phospholipid, an unsaturated fatty acid or its salt or ester, andan antioxidant are homogenized, and the resulting homogenate isdispersed in an aqueous solution containing a protein or its decomposateand a muco-polysaccharide to form a liposomal composite. In this method,if desired, a pH-adjusting agent, a polyhydric alcohol, a saccharide andthe like may be added to the aqueous solution.

(2) A phospholipid, an unsaturated fatty acid or its salt or ester, andan antioxidant are dissolved in an alcohol, a polyhydric alcohol or thelike, and the resulting solution is hydrated with an aqueous solutioncontaining a protein or its decomposate and a muco-polysaccharide toform a liposomal composite. In the step of hydration, a pH-adjustingagent or the like may be added to the system.

(3) Using an ultrasonic wave generator or a French press, aphospholipid, an unsaturated fatty acid or its salt or ester, and anantioxidant are complexed in an aqueous solution containing a protein orits decomposate and a muco-polysaccharide to form a liposomal composite.In this method, if desired, a pH-adjusting agent, a polyhydric alcohol,a saccharide and the like may be added to the aqueous solution.

The liposomal composite dispersion thus prepared according to any of themethods (B) (1) to (3) is, if desired, passed through a filter to dressthe liposomes. Also, if desired, any of polymer substances such ascarboxyvinyl polymer, carboxymethyl cellulose, hydroxyethyl cellulose,xanthane gum, poly(oxyethylene)-poly(oxypropylene) block copolymer,etc.; pH-adjusting agents such as citric acid, salts of citric acid,phosphoric acid, salts of phosphoric acid, triethanolamine, potassiumhydroxide, sodium hydroxide, lactic acid, salts of lactic acid, etc.;polyhydric alcohols such as glycerin, propylene glycol, butylene glycol,etc.; polysaccharides such as salts of alginic acid, esters of alginicacid, etc.; saccharides such as trehalose, glucose, sorbitol, sucrose,etc.; and cholesterol may be added to the liposomal dispersion in orderto improve the stability of the dispersion. The ratio of the unsaturatedfatty acid or its salt or ester to the phospholipid to form liposomes ispreferably from 1/5 to 2/1 by mol, more preferably from 1/2 to 3/2 bymol, as the liposomes comprising them in the ratio falling within thedefined range produce a higher skin-whitening effect.

The skin-whitening cosmetic material of the invention thus produced inthe manner mentioned hereinabove is more effective in reducing orwhitening pigmentation caused on the skin than any other conventionalskin-whitening cosmetic materials, even though the concentration of theunsaturated fatty acid in the cosmetic material of the invention is muchlower than that in the conventional cosmetic materials. In addition, thecosmetic material of the invention is highly safe.

Other Additives:

The skin-whitening cosmetic material of the invention may optionallycontain any of anti-inflammatory agents, UV absorbents, UV reflectors,skin whiteners except the essential component (A), oils, surfactants,moisturizers, animal and vegetable extracts, pH-adjusting agents,colorants, fragrances, preservatives, and chelating agents, within therange not interfering with the effect of the material.

The anti-inflammatory agents include, for example, allantoin,epsilon-aminocaproic acid, glycyrrhetinic acid, glycyrrhizic acid, theirsalts and derivatives, photosensitive substance No. 301, photosensitivesubstance No. 401, diphenhydramine hydrochloride, water-soluble azulenes(salts of 1,4-dimethyl-7-isopropylazulene-2-sulfonic acid), adenosinemonophosphate, lithospermun root extract, ligusticum root extract,mugwort extract, burnet extract, etc. One or more of these may be addedto the composition. The amount of the anti-inflammatory agent to be inthe composition is preferably from 0.01 to 5% by weight.

The UV absorbents include, for example, urocanic acid, ethyl urocanate,oxybenzone, oxybenzone-sulfonic acid, tetrahydroxybenzophenone, sodiumdihydroxydimethoxybenzo-phenone-sulfonate,dihydroxydimethoxybenzophenone, dihydroxybenzophenone, cinoxate, methyldiisopropylcinnamate, octyl methoxycinnamate, glycerylpara-aminobenzoate, amyl para-dimethylaminobenzoate, octylpara-dimethylaminobenzoate, para-aminobenzoic acid, ethylpara-aminobenzoate, butyl-methoxybenzoylmethane, etc. The UV reflectorsinclude, for example, titanium oxide grains, zinc oxide grains, ironoxide grains, silicone-coated grains of those UV reflectors. One or moreof those UV absorbents and reflectors may be added to the composition.The amount of the UV absorbent or reflector to be in the composition maybe from 0.05 to 25% by weight.

The composition of the invention may contain any other skin whitenersexcept the essential component (A). For example, it may contain one ormore of ascorbic acid and its salts and esters, placenta extract, kojicacid and its salts and esters, glucosamine and its salts and esters,azelaic acid and its salts and esters, retinol and its salts and esters,pyridoxine and its salts and esters, tranexamic acid and its salts andesters, arbutin, photosensitive substances, sulfur, 4-hydroxycinnamicacid, ginseng extract, licorice root extract, etc. The amount of theadditional skin whitener to be in the composition may be from 0.1 to10.0% by weight.

EXAMPLES

Now, the invention is described in more detail by means of the followingExamples and Comparative Examples, which, needless-to-say, are notintended to restrict the scope of the invention. Unless otherwisespecifically indicated, “%” in Examples and Comparative Examples is byweight.

Examples 1 to 9, and Comparative Examples 1 to 17

The ingredients shown in Tables 1 and 2 along with their amounts wereformulated into skin-whitening cosmetic materials, which were thenevaluated. The methods of formulating them and the methods of evaluatingthem are mentioned below.

[Formulation of Cosmetic Materials]

The ingredients shown in Tables 1 and 2 were formulated according to themethods mentioned below to prepare cosmetic materials of Examples 1 to 9and Comparative Examples 1 to 17, which were then evaluated.

[Formulation of Cosmetic Materials of Examples 1, 2 and 6, andComparative Examples 1 to 17]

Collagen and sodium chondroitin sulfate were dissolved in purifiedwater, to which was added a mixture of lecithin or hydrogenatedlecithin, the unsaturated fatty acid indicated, and vitamin E, alongwith 1,3-butylene glycol, carboxyvinyl polymer, potassium hydroxide, andmethyl para-hydroxybenzoate, and mixed by stirring them. Thus wereprepared essence samples. [Formulation of Cosmetic Materials of Examples3, 5 and 9, in which was prepared a liposomal composite by Method B]

Lecithin or hydrogenated lecithin, the unsaturated fatty acid indicated,and vitamin E were mixed with 1,3-butylene glycol and homogenized. Next,the resulting homogenate was added to a solution of collagen and sodiumchondroitin sulfate in purified water, and mixed by stirring them. Then,this was processed in a French press to form a liposomal composite. Theresulting liposomal composite was added to a solution of 1,3-butyleneglycol, carboxyvinyl polymer, potassium hydroxide and methylpara-hydroxybenzoate in purified water, and mixed by stirring them. Thuswere prepared essence samples. Formulation of Cosmetic Materials ofExamples 4, 7 and 8, in which was prepared a liposomal composite byMethod A:

Lecithin or hydrogenated lecithin, the unsaturated fatty acid indicated,and vitamin E were dissolved in a solvent such as methylene chloride,and homogenized. Then, purified water was added to the resultinghomogenate, from which the solvent had been removed, and mixed bystirring them. The resulting mixture was processed in a French press toform liposomes. The liposomes were added to a solution of collagen andsodium chondroitin sulfate in purified water. The resulting mixture wasadded to a solution of 1,3-butylene glycol, carboxyvinyl polymer,potassium hydroxide and methyl para-hydroxybenzoate in purified water,and mixed by stirring them. Thus were prepared essence samples.

[Evaluation of Cosmetic Materials]

1. Test for reducing or whitening pigmentation (anti-pigmentation):

Herein used were brown English guinea pigs as test animals. The back ofeach test animal was shaven, and exposed to UV rays (UVB strength: 1J/cm²) twice a week for 2 weeks. After having been left for 1 week, alltest animals had a stable pigmentation portion. Each sample obtained inthe Examples and Comparative Examples was applied to the pigmentationportion of each test animal, once a day for continuous 4 weeks. Duringthis application test, the degree of pigmentation being treated witheach sample was visually observed on the first day of each week, and theeffect of each sample to reduce or whiten pigmentation was evaluatedaccording to the criteria mentioned below. Of some test animals, thelightness (L) of the pigmentation portions being treated with the samplewas measured using a calorimeter.

(Criteria for the degree of pigmentation)

−: The sample had no effect in reducing or whitening pigmentation.

±: The sample had a little effect in reducing or whitening pigmentation.

+: The sample had an effect in reducing or whitening pigmentation in amiddle degree.

++: The sample had effect in reducing or whitening pigmentation in ahigh degree.

2. Test for skin penetrability:

The samples of Example 4, and Comparative Examples 4 and 11 were testedfor the skin penetrability of linoleic acid or linolic acid in thosesamples. Hairless mice were used as test animals herein. The back skinof each test animal was peeled, and stretched in a diffusion cellcontaining a physiological saline solution as the reservoir. While theskin was incubated in the cell at 37° C., 0.5 ml of each sample wasapplied onto the skin. Linoleic acid or linolic acid was extracted fromthe skin as sampled at predetermined time intervals. Then, linoleic acidor linolic acid finally remained in the skin was recovered. The bothwere quantified through high-performance liquid chromatography. Based onthe amount (100) of linoleic acid or linolic acid having finallyremained in the skin, the degree of time-dependent penetration oflinoleic acid or linolic acid into the skin at the sampling time wascalculated.

The data obtained are shown in Tables 1 and 2 and FIGS. 1 and 2.

TABLE 1 Example Ingredients 1 2 3 4 5 6 7 8 9 Linoleic acid or Linolicacid 0.50 0.10 0.05 α-Linolenic acid 0.50 0.05 Eicosapentaenoic acid0.10 Ethyl α-linolenate 0.10 0.05 Linoleic acid monoglyceride 0.50Lecithin 0.40 0.20 0.80 0.20 0.30 0.20 Hydrogenated lecithin 0.20 0.400.80 0.20 Vitamin E 0.05 0.01 0.10 0.05 0.01 0.10 0.05 0.01 0.10Collagen 0.02 0.01 0.50 0.02 0.01 0.50 0.02 0.01 0.50 Chondroitinsulfate 0.01 0.05 0.10 0.01 0.05 0.10 0.01 0.05 0.10 1,3-Butylene glycol5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Carboxyvinyl polymer 0.200.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Sodium hydroxide 0.15 0.15 0.150.15 0.15 0.15 0.15 0.15 0.15 Para-hydroxybenzoate 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 Purified water ad lib. ad lib. ad lib. ad lib.ad lib. ad lib. ad lib. ad lib. ad lib. Effect of anti-pigmentation ++++ ++ ++ ++ ++ ++ ++ ++ % by weight

TABLE 2 Comparative example Ingredients 1 2 3 4 5 6 7 8 9 Linoleic acidor Linolic acid 5.00 1.00 α-Linolenic acid 0.50 Eicosapentaenoic acid1.50 0.90 Ethyl α-linolenate 3.00 Linoleic acid monoglyceride 0.10Linoleic acid triglyceride Lecithin 0.80 Hydrogenated lecithin 0.20Vitamin E 0.10 0.01 Collagen 0.05 0.01 Chondroitin sulfate 0.01 0.051,3-Butylene glycol 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00Carboxyvinyl polymer 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Sodiumhydroxide 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15Para-hydroxybenzoate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05Purified water ad lib. ad lib. ad lib. ad lib. ad lib. ad lib. ad lib.ad lib. ad lib. Effect of anti-pigmentation ++ ++ ++ + − − − + ±Comparative example Ingredients 10 11 12 13 14 15 16 17 Linoleic acid orLinolic acid 0.10 0.05 α-Linolenic acid 0.10 Eicosapentaenoic acid 0.05Ethyl α-linolenate 0.05 Linoleic acid monoglyceride 0.50 0.10 Linoleicacid triglyceride 0.10 Lecithin 0.40 0.20 0.80 Hydrogenated lecithin0.40 0.40 0.20 Vitamin E 0.05 0.10 0.05 0.05 0.10 0.05 Collagen 0.500.01 0.05 0.05 0.10 Chondroitin sulfate 0.01 0.10 0.05 0.10 0.05 0.051,3-Butylene glycol 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Carboxyvinylpolymer 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Sodium hydroxide 0.150.15 0.15 0.15 0.15 0.15 0.15 0.15 Para-hydroxybenzoate 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 Purified water ad lib. ad lib ad lib. ad lib.ad lib. ad lib. ad lib. ad lib. Effect of anti-pigmentation + ± ± ± ± −− − % by weight

As is known from Tables 1 and 2 and FIG. 1, the samples of the Examples,which contained, as the essential ingredients, an unsaturated fatty acidor its derivative, a phospholipid, an antioxidant, a protein or itshydrolyzate, and a muco-polysaccharide, were all found to have asignificant effect in reducing or whitening pigmentation, and these hadno trouble of skin irritations.

As opposed to those, the samples of the Comparative Examples had noeffect in reducing or whitening pigmentation unless the concentration ofthe unsaturated fatty acid or its derivative therein was larger than 1%by weight. In addition, the samples of the Comparative Examples notcontaining any one of the indispensable ingredients of the inventionwere found to have a poor anti-pigmentation effect.

From FIG. 2, it is known that the skin penetrability of the unsaturatedfatty acid in the sample of Example 4, which comprises the liposomalcomposite, is higher by 5 times or more than that in the samples ofComparative Examples 4 and 11. This will indicate the high effect inreducing or whitening pigmentation in the sample of Example 4.

Example 10

Lotion:

Ingredients Amount (%) γ-Linolenic acid 0.1 Glycerin 5.0 Soybeanlecithin 0.35 Vitamin E 0.01 Hydrolyzed elastin liquid 1.0 Sodiumhyaluronate 0.05 Para-hydroxybenzoate 0.05 Ethanol 8.0 Citric acid 0.05Sodium citrate 0.07 Fragrance 0.05 Purified water balance Total 100.0

Formulation of lotion:

Hydrolyzed elastin liquid and sodium hyaluronate were dissolved inpurified water. Apart from this, linoleic acid, soybean lecithin andvitamin E were mixed, and the resulting mixture was added to the aqueoussolution prepared above. To the mixture, added were glycerin, citricacid, sodium citrate, ethanol, methyl para-hydroxybenzoate andfragrance, and well stirred to obtain a lotion.

Example 11

Cream:

Ingredients Amount (%) (A) Corn lecithin 0.40 Eicosapentaenoic acid 0.20Erythorbic acid 0.02 Purified water 10.00 (B) Sodium chondroitin sulfate0.005 Hydrolyzed sodium casein 0.02 Purified water 5.00 (C) Glycerin5.00 dl-Pyrrolidone-carboxylic acid 0.10 Para-hydroxybenzoate 0.05Potassium hydroxide ad lib. (for pH control) Purified water balanceDecaglyceryl monostearate 1.00 (D) Stearic acid 1.00 Cetanol 2.00Glyceryl monostearate 2.00 Squalane 3.00 Total 100.0

Formulation of cream:

A mixture of the phase (A) was mixed with a uniform solution of thephase (B). Then, the phases (C) and (D) were separately dissolved underheat, and the phase (C) was added to the phase (D), mixed and emulsifiedusing an emulsifying machine. Next, the mixed phase (A) was mixed,stirred and cooled to obtain a cream (pH 7.0).

Example 12

Essence:

Ingredients Amount (%) (A) Soybean lecithin 0.40 Linoleic acid 0.10Vitamin E 0.04 Propylene glycol 2.00 (B) Sodium chondroitin sulfate 0.01Para-hydroxybenzoate 0.05 Atelocollagen 0.05 Propylene glycol 1.00Purified water 10.00 (C) Purified water balance Propylene glycol 5.00Carboxyvinyl polymer 0.20 Water-soluble placenta extract 0.10 Potassiumglycyrrhizate 0.10 Sodium hydroxide ad lib. (for pH control) Total100.00

Formulation of essence:

A mixture of the phase (A) was mixed with a uniform solution of thephase (B), using a high-pressure homogenizer, to prepare a liposomalcomposite, which was then mixed with the phase (C) by stirring them toobtain an essence (pH 6.6).

Example 13

Pack:

Ingredients Amount (%) (A) 1,3-Butylene glycol 7.00 Titanium oxide 5.00Talc 5.00 Dermatan sulfate 0.015 Casein 0.04 Purified water ad lib.Para-hydroxybenzoate 0.10 Sodium citrate 0.20 Polyethylene glycol 1.00Hydroxyethyl cellulose 13.00 (B) Phosphatidyl choline 0.60 α-Linolenicacid 0.70 Hamamelis extract 0.005 Purified water 10.00 Total 100.00

Formulation of pack:

The ingredients of the phase (A) were mixed and heated to give a uniformmixture. While cooling the mixture, a mixture of the phase (B) was addedthereto with stirring them to give a pack.

Example 14

Cream mask:

Ingredients Amount (%) (A) Para-hydroxybenzoate 0.20 Glycerin 8.00Purified water balance Triethanolamine ad lib. (for pH control) POE(20)-sorbitan fatty acid ester 2.00 (B) Glycerin monostearate 3.00Self-emulsifying glycerin monostearate 4.00 Stearic acid 5.00 Liquidparaffin 7.00 Glyceryl trioctanoate 4.00 Fragrance 0.10 (C) Egg yolklecithin 0.60 Arachidonic acid 0.10 Vitamin E 0.005 Purified water 10.00(D) Hyaluronic acid 0.005 Hydrolyzed collagen 0.02 Purified water 5.00Total 100.00

Formulation of cream mask:

The phases (A) and (B) were separately dissolved under heat, and thenthe phase (A) was added to the phase (B) and mixed by stirring them togive a uniform mixture. On the other hand, a mixture of the phase (C)was mixed with the phase (D), and the resulting mixture was added to andmixed with the phase (B) by stirring them while the phase (B) wascooled. Thus was obtained a cream mask (pH 6.8).

Example 15

Milky lotion:

Ingredients Amount (%) (A) 1,3-Butylene glycol 5.00 Purified waterbalance Para-hydroxybenzoate 0.30 Decaglyceryl stearate 2.00Carboxyvinyl polymer 0.10 Potassium hydroxide ad lib. (for pH control)Citric acid 0.50 (B) Liquid paraffin 5.00 Stearic acid 1.00 Glycerinmonostearate 2.00 Self-emulsifying glycerin monostearate 1.00 Squalane3.00 (C) Phosphatidyl ethanolamine 0.06 Phosphatidyl serine 0.081Sphingomyelin 0.108 Ethyl linoleate 0.20 EDTA 0.05 Purified water 10.00(D) Sodium chondroitin sulfate 0.05 Keratin 0.02 Purified water 5.00Total 100.00

Formulation of milky lotion:

The phases (A) and (B) were separately stirred under heat to givemixtures, and the mixture of the phase (A) was added to that of thephase (B) and further mixed by stirring them. On the other hand, theingredients of the phase (C) were processed in a French press to formliposomes, which were then filtered to dress them. Then, the liposomeswere added to the phase (D) to prepare a liposomal composite. Thisliposomal composite was added to the phase (B) while the phase (B) wascooled. Thus was prepared a milky lotion (pH 6.9).

Example 16

Face wash:

Ingredients Amount (%) (A) Lauric acid 6.00 Myristic acid 10.00 Stearicacid 20.00 Thick glycerin 10.00 Polyethylene glycol 400 10.00Polyethylene glycol 6000 10.00 Polyethylene glycol distearate (150 EO)5.00 Purified water balance Potassium hydroxide ad lib. (for pH control)Para-hydroxybenzoate 0.20 Sodium edetate 0.10 (B) Lecithin 0.40 VitaminE 0.10 Ethyl α-linolenate 0.20 Purified water 10.00 (C) Sodiumchondroitin sulfate 0.01 Hydrolyzed collagen 0.03 Purified water 5.00Total 100.00

Formulation of face wash:

The ingredients of the phase (A) were mixed and dissolved under heat.The phases (B) and (C) were separately mixed to give uniform mixtures,and the phase (B) was added to the phase (C). While the phase (A) wascooled, the phase (C) was mixed and stirred with the phase (A). Thus wasprepared a face wash (pH 9.6).

Example 17

Cream mask:

Ingredients Amount (%) (A) Para-hydroxybenzoate 0.20 Glycerin 8.00Purified water balance Triethanolamine ad lib. (for pH control) POE(20)-sorbitan fatty acid ester 2.00 (B) Glycerin monostearate 3.00Self-emulsifying glycerin monostearate 4.00 Stearic acid 5.00 Liquidparaffin 7.00 Glycerin trioctanoate 4.00 Fragrance 0.10 (C) Egg yolklecithin 0.60 Linoleic acid monoglyceride 0.10 Vitamin E 0.005 Sodiumhydroxide ad lib. (for pH control) 1,3-Butylene glycol 1.00 Purifiedwater 10.00 (D) Hyaluronic acid 0.005 Hydrolyzed collagen 0.02 Purifiedwater 5.00 Total 100.00

Formulation of cream mask:

The phases (A) and (B) were separately dissolved under heat to giveuniform mixtures. Then, the phase (B) was added to the phase (A) andmixed by stirring them to give a uniform mixture. The ingredients, eggyolk lecithin, linoleic acid monoglyceride and vitamin E werehomogenized, and then hydrated with an aqueous solution (pH 6)containing sodium hydroxide and 1,3-butylene glycol to form liposomes(of the phase (C)). The resulting phase (C) was mixed with the phase(D), and added to and mixed with the phase (B) by stirring them whilethe phase (B) was cooled. Thus was prepared a cream mask (pH 6.8).

Example 18

Essence:

Ingredients Amount (%) (A) Egg yolk lecithin 0.80 Docosahexaenoic acid0.40 Vitamin C 0.04 Purified water 10.00 (B) Chondroitin sulfate 0.01Para-hydroxybenzoate 0.05 Hydrolyzed ethyl collagen 0.05 Purified waterbalance Propylene glycol 5.00 Carboxyvinyl polymer 0.20 Potassiumhydroxide ad lib. (for pH control) Total 100.00

Formulation of essence:

The ingredients, egg yolk lecithin, docosahexaenoic acid and vitamin Cwere mixed in water and ultrasonicated to form liposomes (of the phase(A)). This phase (A) was added to and mixed with a uniform mixture ofthe phase (B) by stirring them to obtain an essence (pH 6.6).

All the samples of Examples 10 to 18 were found to have an excellenteffect in reducing or whitening pigmentation, like the samples ofExamples 1 to 9.

INDUSTRIAL APPLICABILITY

The skin-whitening cosmetic material of the invention contains a reducedamount of unsaturated fatty acids, and irritates little the skin towhich it has been applied. In addition, the material is highly safe andhas an excellent effect in reducing or whitening pigmentation.

What is claimed is:
 1. A skin-whitening cosmetic material comprising;(A) at least one member selected from the group of compound consistingof unsaturated fatty acids having from 18 to 22 carbon atoms and havingfrom 2 to 6 double bonds in the molecular structure, and theirderivatives, wherein the amount of said unsaturated fatty acids andtheir derivatives is from 0.01 to 0.7% by weight of the total amount ofthe material, (B) a phospholipid, (C) an antioxidant in an amount offrom 0.0005 to 0.5% by weight, (D) at least one member selected from thegroup of compounds consisting of proteins and their hydrolyzates, and(E) chondroitin sulfate.
 2. A skin-whitening cosmetic materialcomprising a liposomal composite that contains the following: (A) atleast one member selected from the group of compounds consisting ofunsaturated fatty acids having from 18 to 22 carbon atoms and havingfrom 2 to 6 double bonds in the molecular structure, and theirderivatives, wherein the amount of said unsaturated fatty acids andtheir derivatives is from 0.01 to 0.7% by weight of the total amount ofthe material, (B) a phospholipid, (C) an antioxidant in an amount offrom 0.0005 to 0.5% by weight, (D) at least one member selected from thegroup of compounds consisting of proteins and their hydrolyzates, and(E) chondroitin sulfate.
 3. The skin-whitening cosmetic material asclaimed in claim 1, wherein the phospholipid is at least one memberselected from the group of compounds consisting of soybean lecithin, eggyolk lecithin, hydrogenated soybean lecithin and hydrogenated egg yolklecithin.
 4. The skin-whitening cosmetic material as claimed in claim 1,wherein the protein or its hydrolyzate is at least one member selectedfrom the group of compounds consisting of collagen, elastin and theirhydrolyzates, and salts and esters of their hydrolyzates.
 5. Theskin-whitening cosmetic material as claimed in claim 1, wherein thechondroitin sulfate is present in an amount of from 0.0005 to 0.5% byweight.
 6. The skin-whitening cosmetic material as claimed in claim 2,wherein the phospholipid is at least one member selected from the groupof compounds consisting of soybean lecithin, egg yolk lecithin,hydrogenated soybean lecithin and hydrogenated egg yolk lecithin.
 7. Theskin-whitening cosmetic material as claimed in claim 2, wherein theprotein or its hydrolyzate is at least one member selected from thegroup of compounds consisting of collagen, elastin and theirhydrolyzates, and salts and esters of their hydrolyzates.
 8. Theskin-whitening cosmetic material as claimed in claim 2, wherein thechondroitin sulfate is present in an amount of from 0.0005 to 0.5% byweight.
 9. The skin-whitening cosmetic material as claimed in claim 2,wherein the liposomal composite is prepared by forming liposomes inwater as a result of mixing the following: (A) at least one memberselected from the group of compounds consisting of unsaturated fattyacids having from 18 to 22 carbon atoms and having from 2 to 6 doublebonds in the molecular structure, and their derivatives, (B) aphospholipid, and (C) an antioxidant, followed by mixing the resultingliposomes with an aqueous solution containing the following: (D) atleast one member selected from the group of compounds consisting ofproteins and their hydrolyzates, and (E) at least one member selectedfrom the group of compounds consisting of muco-polysaccharides and theirsalts.
 10. The skin-whitening cosmetic material as claimed in claim 2,wherein the liposomal composite is prepared by forming liposomes in anaqueous solution containing the following: (D) at least one memberselected from the group of compounds consisting of proteins and theirhydrolyzates, and (E) at least one member selected from the group ofcompounds consisting of muco-polysaccharides and their salts, saidliposomes comprising the following: (A) at least one member selectedfrom the group of compounds consisting of unsaturated fatty acids havingfrom 18 to 22 carbon atoms and having from 2 to 6 double bonds in themolecular structure, and their derivatives, (B) a phospholipid, and (C)an antioxidant.